Preparation of halogen substituted polycyclic epoxides



United States Patent O PREPARATION OF HALOGEN SUBSTITUTED POLYCYCLIC EPOXIDES John P. Luvisi and Louis Schmerling, Riverside, 111., as-

signors to Universal Oil Products Company, Des Plaines, 111., a corporation of Delaware No Drawing. Application June 29, 1955 Serial No. 518,996

8 Claims. (Cl. 260-348) This application is a continuation-impart of our copending application Serial No. 399,630, filed December 21, 1953, now abandoned.

This invention relates to a process for preparing halogenated substituted polycyclic epoxides, and more particularly, to a process for preparing hexachloro-substituted pentacyclic epoxides.

An object of this invention is to prepare polyhalo substituted polycyclic epoxides. A further object of this invention is to prepare novel compositions of matter comprising hexachloro substituted pentacyclic epoxides which are useful as insecticides and miticides.

One embodiment of this invention resides in a process which comprises reacting an unsaturated 1,2-epoxide with a conjugated cyclic diene, subsequently condensing the reaction product with a polyhalocycloalkadiene, and recovering the resultant condensation product.

A specific embodiment of the invention resides in a process which comprises reacting an unsaturated 1,2- epoxide with cyclopentadiene at a temperature in the range of from about 150 to about 190 C. and at a superatmospheric pressure to form an epoxyalkylbicyclic compound, subsequently condensing said compound with hexachlorocyclopentadiene, and recovering the resultant epoxyalkylhexachlorodimethanonaphthalene.

A more specific embodiment of the invention is found in a process which comprises reacting butadiene monoxide with cyclopentadiene at a temperature in the range of from about 150 to about 190 C. and at a superatmospheric pressure to form 5-epoxyethylbicyclo [2.2.1]- Z-heptene, subsequently condensing said heptene with hexachlorocyclopentadiene, and recovering the resultant 2 (epoxyethyl) 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8aoctahydro-1,4,5,8-dimethanonaphthalene.

Yet another specific embodiment of the invention resides in a new composition of matter comprising Z-(epoxyethyl)-5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro- 1,4,5,8-dimethanonaphthalene.

Other objects and embodiments will be referred to in the following further detailed description of the invention.

It has now been discovered that compounds which are prepared by condensing conjugated polyhalocycloalkadienes with the reaction products of conjugated cycloalkadienes and unsaturated epoxides exhibit insecticidal and miticidal activity. In the process of this invention conjugated cyclic dienes are first reacted with unsaturated epoxides, and the products therefrom are then condensed with polyhalocyclicalkadienes toform the desired compounds.

- Conjugated cyclic dienes which may be used in this reaction include 1,3-cyclopentadiene (usually, and hereinafter, referred to merely as cyclopentadiene), 1,3-cyclohexadiene, 1,3-cycloheptadiene, etc., alkyl substituted cyclic dienes such as S-methylcyclopentadiene, 5,5-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1' ethylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,2-diethylcyclopentadiene, etc., l-methyl-1,3-cyc1ohexadiene, .l-.

2,882,279 Patented Apr. 14, 1959 in which R is an aliphatic, cyclic, bicyclic or polycyclic hydrocarbon radical containing at least one non-aromatic double bond and R is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, bicyclm alkyl, and aryl radicals. Such epoxy compounds may be referred to as unsaturated 1,2-epoxides, the designation 1,2-indicating that the oxygen is attached to adjacent carbon atoms. Typical specific compounds of the unsaturated 1,2-epoxides include 3,4-epoxy-1-butene (butadiene monoxide), 3,4-epoxy-2-methyl-l-butene, 3,4-epoxy- 2-ethyl-l-butene, 4,5-epoxy-2-pentene, 4,5-epoxy-1-pentene, 1,2-epoxy-3-hexene, 3,4-epoxy-1-hexene, etc., 3,4- epoxy-l-cyclohexene, 4,5-epoxy-l-cyclohexene, etc., 1 vinyl-1,2-epoxycyclohexane, etc., '3-(epoxyethyl)cyclohexene, etc., 5,6-epoxy-1,3-hexadiene, 5-(epoxyeth'yl)bicyclo[2.2.1]-2-heptene, etc.

The condensation of an unsaturated 1,2-epoxide with a conjugated cyclic diene in accordance with this invention occurs at temperatures ranging from about 50 C. to about 250 C. and preferably within the range of from C. to about 200 C. In addition, the reaction proceeds at atmospheric or superatmospheric pressures ranging to about atmospheres or more, the preferred range being from about 1 to about 75 atmospheres. The superatmospheric pressures used in this reaction may be provided by the introduction of an inert gas such as nitrogen into the closed reaction chamber. The reaction conditions under which this condensation will be carried out will depend largely upon the particular reactants undergoing reaction.

The proportion of conjugated cyclic dienes to unsaturated epoxides will depend upon the particular condensation product desired. For example, when the epoxide of a bicyclic hydrocarbon is desired, the molar proportion of conjugated cyclic diene to unsaturated epoxide will be 1:1. The reaction will proceed chiefly according to the following equation:

However, if a pentacyclic derivative is desired, as chief product, 2 moles of the conjugated cyclic diene are reacted with 1 mole of olefinic epoxide, while, if an heptacyclic epoxide is desired, 3 moles of a conjugated cyclic diene is reacted with 1 mole of olefinic epoxide.

The polycyclic epoxides which result from the above metioned reaction are then condensed with a conjugated polyhalocycloalkadiene. Typical specific exemplary compounds of these halogen-substituted cyclic dienes include 5-chlorocyclopentadiene, 5,5-dichloro-cyclopentadiene, S-bromocyclopentadiene, 5,5-dibromocyclopentadiene, 1,2,4-trichlorocyc1opentadiene, 1,5,5-trichlorocyclopentadiene, 1,4,5,5-tetrachlorocyclopentadiene, 1,2,3, 5,5 pentachlorocyclopentadiene, hexachlorocyclopentadiene, hexabromocyclopentadiene, etc., 1-chloro-1,3-' cyclohexadiene, 1,2 dichloro-1,3 cyclohexadiene, 1- bromo-1,3-cyclohexadiene, octachloro-1,3-cyclohexadiene;

, etc., l-chloro-l,3-cycloheptadiene, 1,2'dichloro-1,3-'cycl0-' tenement, talseeic'hnraheptadirne, .l,2,3,-,4 ,5,,5-.hexachloro 1,3 cycloheptadiene, decachloro 1,3 cycloheptadiene, etc.

The condensation-of the polyhalocycloalkadiene "with IhepQLYQYGIic epoxide *is also carried out:at temperatures ranging from about 50 C. to about 1250" :C. and preferably within the range of from 80 :C.-to:about .200" C. Ill-addition, the reactiomproceeds at atmospherictor superatmospheric pressuresranging to-about 100 atmospheres or-more, the preferred range being from aboutl to about 7. 5 atmospheres.

Examples of the halogen-substituted polycyclic -epoxides which result from this .condensation, and constitute new compositions of matter, include Z-(epoxyethyD- 5,6,7,8,9,9-hexachloro l,2,3;4;4aj5,8,8a-octahydro-1,4,5, S-dimethanonaphthalene, -2 1 ,Z-epoxypropyl -5,6,7,8,9, 9ehexachloro-1,2,3,4,4a,5,8,8a-octahydro-l,4,5,8 dimethanonaphthalene, f2-l(1 ,Z-epoxybu'tyl '-5 ,6, 7 ,8,9.,9-.hexachloro-.l',2.,'3,4,4a, 5,8',8aeoctahydro .1,4,5,8 .dimethanonaph- 'thalene, 2-.(1,2-'epoxypr.opyl) 3-methyl-5,6IZ,.8,9,'9 hexachlorod,2,3,4,4a,5;8,'8a1octahydro 1,4,S,8 'dimethanonaphthalene, 2- ('l,'2-cpoxye2=methylpropyl) 5,63,89,9- hexachloro-1',2;3,4,4a;58;8aeoctahydro l,4,5,8 -.dimeth anonaphthalene, "2-,(l,'2 epoxycyclohexyl) "5,6,73,93- hexachloro-l,2;3,4,4a,S,'8,8a-octahydro-- 1,4,5 ,"8 dimethanonaphthalene. It isto be understood that the above mentioned compounds are only examples of the class of compounds which maybe prepared :accordingto: thejprocess of the invention,-.and that said process is not necessarily limited thereto.

"The process of this invention ,mayibe effected in any suitable manner and may be either-a batch or continuous typeof'operation. When a batch type operation is used, aIquantityofthestarting material, namely the conjugated cyclictdiene and the unsaturated 1,2-epoxide is placed in a reaction vesselfsuch as a reaction vessel such as a pressure autoclave andreactedatsuperatrnospheric pressure and elevated temperatures hereinbefore ,set forth. A suitable means of providing the ,a'foresaidsnperatmospheric pressureis by thefintroduction of an inert gas such as nitrogen or hydrogen into'the reaction vessel. Alternative'ly the pressure maybe the vapor pressure of the reactants. The reactor islheated to-the desired temperature and the reaction proceeds toward completion, after which the reactorandthe contents thereof are .allowedto cool to room' temperature and the pressurereduced. The reaction product is then separated from the unreacted material by conventional means, for example, by fractional distillation, fractional crystallization, etc., while the unreactedstarting materials may be recycled for further use. The reaction-productmaythen be returned to the reaction vessel or placed in a second reaction vessel along with .the. polyhalocycloalkadiene such as hexachlorocyclopentadiene and heated to a predetermined temperature. At the end of the desired residencetime the vessel and contents are cooled to room temperature and the desired condensation product is'aseparated by conventional means hereinbe'fore set'forth from any unreacted feedstock.

Another method of operation of the present process is of the continuous type. In thismethod the reactants are admitted by separate means or as a mixture, into a reactorwhich fism'aintained at the proper condensation conditions of "temperature and pr'es'sure. The reaction conjugated were nieces iann-shennsamrated .l, 2-epoxide may berecycled for reuse as a, portion of the starting materials.

The reaction product is then continuously charged to a second reactor which is also maintained at the proper operating conditions of temperature and pressure. The polyhalocycloalkadiene is also'continuously charged to the second :reactor in a separate stream, .or commingled with the epoxy polycyclic compound prior to admission. The condensation product is also continuously withdrawn, separated 'from unrea'ctedfeed stock and purified by-ceinventional means, while the unreacted feed .stock :is ire cycled.

The condensationreaction of the gpresentdnvention may be carried outinthe presence of inert organic solvents such as aromatic and alkylated aromatic compounds including benzene, toluene, xylene, etc., saturated aliphatic alcohols including ethanol, propanol, butanol, etc., orethers including diethyl'ether, dipropyl ether, methyl ethyl-ether, methyl :propyl ether, diphenyl .ether diethyI phenyl ether, etc. v p

:The physical properties of the .present adduc'tsof a polyhalocycloalkadiene and the reaction :product of s conjugated cyclic diene and an unsaturated epoxide,iand the effects they have on entomological forms ofdifemake them.;-particularlydesirable as insecticides and miticides, the particular compounds having many of the features desired for this purpose. They are for example, toxic to insects and' mites which are destructive of ,plant life andmaterials normally subject to insect infestation, their toxic effects being manifested by contact of thepoiso'n with the-insect. The insecticides and miticides-scou' prising .thegpresent-compounds are effective against chewing as 'WQHBES'SUCI'I types of insects. The-compounds are-sufficiently volatile :so that when applied to plant life-intended for subsequent human consumption the plant's, when harvested and after allowing a reasonable time *for evaporation of (the applied insecticide therefrom, retain noneof the toxicant to prevent use of the plant forfood. On the other hand, the compounds are of 'sufliciently limited volatility to be retained on the insect or the mite for the time required to accomplish the toxic effects of thecompound. The volatility and retentive capacity of the compounds may be varied at will by combining them with suitable fixing agents which reduce or promote their volatilization, as desired. Thus, the compounds may be dissolved in a suitable high boiling solvent such as a mineral'or vegetable oil, petroleum, etc.; a waxsuch as paraffin wax, beeswax; a high molecular alcohol or ether such as myricyl alcohol, dibutyl ether, etc.; or they may be emulsified with water or combined with an .oil and emulsified with water by the addition of an emulsifying agent such as a surface active agent to the mixture :of components. The latter solvents and dispersants may also bezemployed for the specific purpose of reducing the concentration of the active components to the desired level in a specific insecticidal formulation. The particu lar formulation of activecomponents in composition with tbe'e'solvent or dispersant will depend upon its application. A- composition containing ashigh 215 20% 'of active 60mponent'may be preferred in some instances where deep penetration of the insecticide is desired, as in :the treatment of fibrous materials for extinction of a particular infestation. For other purposes, the required concentration of active component in the formulation may bees low tas=0;1:%

..-In='utilizin'g the present fin'secti'cidaland mineidal *e'on'rpounds against most insects and mites, a compound' o'o'htaining from about 0.1 to about 5% 'by Weight of active component is highly effective. The choice of the mos; desirable solvent or dispersant further depends upon the method utilized to apply the insecticidalcompound to the infected Larticl'e. Fnrexample, a lowmolecular weight, normally-gaseous carrying agent for :the active composition, :such as propane, .but ane, the Piecing-em,

-taining,thc. .insecticide. .Up on .release of pressure fromthe bomb, the liquified carrier vaporizes and suspends a EXAMPLE I A mixture of 50 g. of cyclopentadiene and 30 g. of butadiene monoxide was heated at a temperature ranging from 150 to 190 C. during a period of 4.5 hours in a glass-lined rotating autoclave of 850 cc. capacity, the autoclave having been placed under an initial nitrogen pressure of 50 atmospheres. At the end of this time the autoclave and the contents thereof was allowed to cool to room temperature, the reaction product taken up in toluene, and distilled under reduced pressure yielding the following fractions: (1) 24 g. of a product having a boiling point of 69-70 C. at mm. (or about 191-192" C. at 760 mm.); (2) 16 g. of a product having a boiling point of 117-12l C. at 3 mm. (or about 286-290 C. at 760 mm.); and (3) 2 g. of a product having a boiling point of about 165-180" C. at 3 mm. (or about 350-370 C. at 760 mm.) and a melting point of about 105 C. The above mentioned fractions were analyzed and it was found that they consisted of the product of the reaction of butadiene monoxide with 1, 2 and 3 moles respectively of cyclopentadiene and that they had the following formulas respectively:

1 iii I (Ii-7C i i U Fraction 1 was S-(epoxyethyl)bicyclo[2.2.1]-2-heptene.

Analysis of fraction 1.Found: C, 79.95; H, 9.12. Calculated for C l-I 0: C, 79.37; H, 8.88.

Analysis of fraction 2.Found: C, 86.60; H, 9.03. Calculated for C H O: C, 83.12; H, 8.97.

Analysis of fraction 3.Found: C, 84.30; H, 9.03. Calculated for C H O: C, 85.02; H, 9.01.

10 g. of S-(epoxyethyl)bicyclo[2.2.1]-2-heptene which was prepared as described above and 20 g. of hexachlorocyclopentadiene were admixed along with 15 g. of toluene and the solution heated under reflux conditions at a temperature of approximately 124 C. for a period of 14 hours. The reaction product was subjected to fractional distillation under reduced pressure and 18 g. of a liquid adduct having a boiling point of 403 to 406 C. at 760mm. pressure was obtained. That this adduct was the desired 2-(epoxyethyl)-5,6,7,8,9,9-hexachloro-1,2,3,4, 4a,5,8,8a-octahydro-1,4,5,S-dimethanonaphthalene was indicated by its analysis.

Found: C,41.28; H, 3.21; CI, 52.04. Calculated for cucnclgoi C, 41.11; H, 2.96; C], 52.02.

EXAMPLE II The insecticidal and miticidal activity of the type of compound prepared according to the invention was determined using house flies, pea aphids, red spider mites and as an emulsifying agent.

Peroe Table I Red Spider 2-Spotted I mite, 5 days mlte, 5 days Houseflies, 24 hours Concentration, percent nt Kill b 100 I Ovlcldal. b 35% kill at 0.1% concentration.

We claim as our invention:

1. A process which comprises reacting butadiene monoxide with cyclopentadiene at a temperature of from about 50 to about 250 C. to form 5-(epoxyethyl)bicyclo[2.2.1]-2-heptene and subsequently condensing said heptene with hexachlorocyclopentadiene at a temperature of from about 50 to about 250 C. to form 2- (epoxyethyl) 5,6,7,8,9,9 hexachloro 1,2,3,4,4a,5,8, Sa-octahydro-1,4,5,8-dimethanonaphthalene.

2. A process which comprises reacting 3,4-epoxy-1- pentene with cyclopentadiene at a temperature of from about 50 to about 250 C. to form 5-(1,2-epoxypropyl)bicyclo[2.2.1l-2-heptene and subsequently condensing said heptene with hexachlorocyclopentadiene at a temperature of from about 50 to about 250 C. to form 2 (1,2 epoxypropyl) 5,6,7,8,9,9 hexachloro 1,2, 3,4,4a,5,8,8a-octahydro-1,4,5,S-dimethanonaphthalene.

3. The compound 2 (epoxyethyl) 5,6,7,8,9,9 hexachloro 1,2,3,4,4a,5,8,8a octahydro 1,4,5,8 dimethanonaphthalene.

4. A process which comprises reacting at a temperature of from about 50 to about 250 C. an unsaturated 1,2-epoxide selected from the group consisting of 3,4-epoxy-1-butene, 3,4 epoxy 2 methyl -,1 butene, 3,4 epoxy- 2 ethyl 1 -butene, 4,5 epoxy 2 pentene, 4,5 epoxyl-pentene, 1,2-epoxy-3-hexene, 3,4-epoxy-1-hexene, 3,4- epoxy-l-cyclohexene, 4,5-epoxy-1-cyclohexene, l-vinyl- 1,2-epoxy-cyclohexane, 3-(epoxyethyl)-cyclohexene, 5,6- epoxy-l,3-hexadiene, S-(epoxyethyDbicyclo[2.2.1]-2-hep tene with a conjugated cyclic diene selected from the group consisting of cyclopentadiene, cyclohexadiene, cycloheptadiene and their alkyl derivatives, and condensing the resultant reaction product at a temperature of from about 50 to about 250 C. with a polyhalocycloalkadiene in which the halogen is selected from the group consisting of chlorine and bromine and in which the cycloalkadiene component is a member of the group consisting of cyclopentadiene, cyclohexadiene and cyclohep tadiene.

5. The process of claim 4 further characterized in that each of said reactions is eflfected at a temperature of from about 80 C. to about 200 C.

6. A process which comprises reacting cyclopentadiene at a temperature of from about 50 to about 250 C. with an unsaturated 1,2-epoxide selected from the group consisting of 3,4-epoxy-l-butene, 3,4-epoxy-2-methyl-l-butene, 3,4-epoxy-2-ethyl-l-butene, 4,5-epoxy-2-pentene, 4,5-epoxy-1-pentene, 1,2-epoxy-3-hexene, 3,4-epoxy-1- hexene, 3,4-epoxy-l-cyclohexene, 4,5-epoxy-1-cyclohexene, l-vinyl-1,2-epoxy-cyclohexane, 3-(epoxyethyl)cyclohexene, 5,6-epoxy-1,3-hexadiene, 5-(epoxyethyl)bicyclo[2.2.1]-2-heptene, and condensing the resultant reac' tion product with hexachlorocyclopentadiene at a temperature of from about 50 to about 250 C.

7. The process of claim 6 further characterized in that the first-mentioned reaction is efiected at a temperature of from about C. to about C. and the secondmentioned reaction is effected at a temperature of from Z-spotted mites. A solution of Z-(epoxyethyl)-5,6,7,8,9,9- 75 about 80 C. to about 200 C. 

8. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF 2 - (EPOXYETHYL) - 5,6,7,8,9,9 - HEXACHLORO - 1,2,3,4, 4A,5,8,8A - OCTAHYDRO - 1,4,5,8, - DIMETHANONAPHTHALENE, 2 - (1,2, - EPOXYPROPYL) - 5,6,7,8,9,9, - HEXACHLORO - 1,2,3 4,4A,5,8,8A - OCTAHYDRO - 1,4,5,8, - DIMETHANONAPHTHALENE, 2 - (1,2-EPOXYBUTY) - 5,6,7,8,9,9 - HEXACHLORO - 1,2,3, 4,4A,5,8,8A - OCTAHYDRO - 1,4,5,8 - DIMETHANONAPHTHALENE, 2 - (1,2-EPOXYPROPYL) - 3 - METHYL - 5,6,7,8,9,9 - HEXACHLORO - 1,2,3,4,4A,5,8,8A - EPOXY - 2 - METHYLPROPYL -5, ANONAPHTHALENE, 2 - (1,2, -EPOXY -2 - METHYLPROPYL - 5, 6,7,8,9,9 - HEXACHLORO - 1,2,3,4,4A,5,8,8A - OCTAHYDRO1,4,5,8-DIMETHANONAPHTHALENE, AND 2-(1,2,-EPOXYCYCLOHEXYL - 5,6,7,8,9,9 - HEXACHLORO - 1,2,3,4,4A,5,8,8A - OCTAHYDRO-1,4,5,8-DIMETHANONAPHTHALENE. 